DE602004007068T2 - Polyamideimide resin, process for its preparation, polyamideimide composition, film-forming material prepared therefrom and adhesive for electronic parts - Google Patents

Abstract

The present invention provides a resin and a resin composition having low elasticity and being excellent in flexibility while being excellent in heat resistance, electric characteristics and adhesivity, a film-forming material comprising the resin or resin composition, and an adhesive for electronic parts. The resin of the present invention is a polyamideimide resin comprising a structural unit represented by the following general formula (1) and at least one of the structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (3). The number k of the structural unit represented by the general formula (1), the number m of the structural unit represented by the general formula (2), and the number n of the structural unit represented by the general formula (3) contained in the polyamide resin satisfy the relation of 0 < m/(k + m + n) ≤ 0.1, wherein the resin contains a polyamideimide copolymer with a number average molecular weight of 2000 to 50000: <CHEM> (wherein, Ar1 and Ar2 each represent an aromatic group that may be substituted) <CHEM> (wherein, Ar2 is defined as described above, and a, b and c each are an integer of 0 to 100 with the relations of the ratio a/b of 0/1 to 1/0, the ratio (a + b)/c of 1/0 to 0/1, and the sum (a + b + c) of 1 to 100) <CHEM> (wherein, Ar2 is defined as described above, and d is an integer of 1 to 100).

Description

The The present invention relates to a polyamide-imide resin a process for producing the polyamideimide resin on a polyamideimide resin composition, on a film-forming material and on an adhesive for electronic Parts using the polyamideimide resin or the polyamideimide resin composition.

Polyamide resins, Polyamide-imide resins and polyimide resins have been in recent years in the field of electronic materials instead of epoxy resins as heat resistant Resins have been used, which are particularly advantageous in terms of their heat resistance, their electrical properties, their adhesiveness, their hygroscopicity and their Processing suitability. Without consideration their excellent properties, as just described, However, these resins are highly elastic, so that in the case where they are used as coating films, only a bad one adhesiveness on the substrate, due to its in a high Measure rigid Resin structure while the softness and pliability of cured films because of their low flexibility only insufficient fail.

To solve these problems, there is proposed an aromatic polyamide-acrylonitrile-butadiene copolymer which is prepared to have a low modulus of elasticity by giving flexibility to the resin by using carboxylic acid-terminated acrylonitrile-butadiene (cf. Japanese Patent Application No. 02-245032 and 03-47836 ). The polyamide polymer contained in the polyamide resin has a flexibility given by the polymer skeleton due to a structural unit derived from a butadiene-containing dicarboxylic acid. Therefore, a coating film obtained in this way has high elasticity and therefore can have markedly improved adhesiveness and flexibility.

The after the conventional However, polyamide resin disclosed in the prior art has a problem thereby on that it is due to the lagging ionic impurities a decrease in the insulating properties records; Impurities ranging from a phosphorus based condensing agents are derived in the polymer, because the Polymer in the presence of the phosphorus-based condensing Is polymerized by means.

Accordingly, there is an object of the invention therein, a resin and a resin composition with a low elasticity and to deliver with an outstanding feature in terms of flexibility, while that Resin and the resin composition are excellent both in terms of on their heat resistance, theirs electrical properties and their adhesiveness as well as their property as a film-forming material containing the resin or the resin composition includes, as well as an adhesive for electronic parts.

The The present inventors have noted that the polyamide-imide resin has excellent properties Features, about about Heat resistance, a low hygroscopicity and excellent electrical properties, especially excellent Insulation properties when compared to polyamide resins.

The Inventors have sought to find aromatic isocyanate compounds to use as starting materials, with regard to switching off the formation of eliminating components in the polymerization process, to reduce the content of impurities in the polymer. The aromatic isocyanate compound is known to have various bonds because it is based on different nucleophiles high reactivity a reaction is received. An imide compound is obtained by heating due to a reaction between the aromatic isocyanate compound and an acid anhydride, and an amide compound is obtained one due to a reaction between the aromatic isocyanate compound and a carboxylic acid.

The Inventors hereof have the reactions described above on a reaction of an acidic dianhydride and an acrylonitrile butadiene with terminal carboxylic acids applied to an aromatic diisocyanate, and they have found out that it is possible is to produce the polyamideimide resin, which has an excellent property in terms of flexibility features, while the formation of eliminating components in the polymerization process repressed to reduce the content of impurities in the polymer to reduce. Accordingly, the The present invention has been completed on the basis of these studies.

(wobei ein jedes Ar₁ und Ar₂ eine aromatische Gruppe darstellt, welche substituiert sein kann),

(wobei Ar₂ so definiert ist wie dies oben beschrieben worden ist und ein jedes a, b und c eine ganze Zahl von 0 bis 100 darstellt, wobei die Relationen des Verhältnisses a/b in dem Bereich von 0/1 bis 1/0, des Verhältnisses (a + b)/c in dem Bereich von 1/0 bis 0/1 und der Summe (a + b + c) liegt in dem Bereich von 1 bis 100 liegen),

(wobei Ar₂ so definiert ist wie dies oben beschrieben worden ist und d eine ganze Zahl von 1 bis 100 darstellt).According to one aspect of the present invention, there is provided a polyamideimide resin which has a structural unit represented by the following general formula (1) and at least one structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3) and which contains a polyamide-imide copolymer having a number-average molecular weight of 2,000 to 50,000. Here, the number k of the structural unit represented by the general formula (1) satisfies the number m of the structural unit represented by the general formula (2) and the number n of the structural unit represented by the general formula (3 ), which are contained in the polyamide resin, the relationship 0 <m / (k + m + n) ≦ 0.1,

(wherein each of Ar ₁ and Ar _{2 represents} an aromatic group which may be substituted),

(wherein Ar ₂ is defined as described above and each of a, b and c represents an integer of 0 to 100, wherein the ratios of the ratio a / b are in the range of 0/1 to 1/0, the ratio (a + b) / c in the range of 1/0 to 0/1 and the sum (a + b + c) is in the range of 1 to 100),

(wherein Ar ₂ is defined as described above and d represents an integer of 1 to 100).

There in the polyamide-imide resin according to the present invention Invention contained copolymer having a structural unit, the from the butadiene-containing dicarboxylic acid in the skeleton thereof has derived, the modulus of elasticity of the resulting, hardened Resin to make the resin so that it is an excellent Has property of adhesiveness and flexibility. In addition is the resin excellent in the insulating properties and the hygroscopic so-called 'reflow' properties, if one uses the same thing the resin compares in which the polyamide resin is used.

(wobei Ar₂ so definiert ist wie dies oben beschrieben worden ist),

(wobei Ar₁ so definiert ist wie dies oben beschrieben worden ist),

(wobei a, b und c so definiert sind wie dies oben beschrieben worden ist),

(wobei d so definiert ist wie dies oben beschrieben worden ist).According to another aspect of the present invention, there is provided a process for producing the polyamideimide resin, comprising the steps of: obtaining the structural unit represented by the general formula (1) by imidizing by means of a decarboxylation reaction between an aromatic diisocyanate represented by the following general formula (4), and an aromatic tetracarboxylic acid dianhydride represented by the following general formula (5); obtaining the structural unit represented by the general formula (2) by amidating by means of a decarboxylation reaction between an aromatic diisocyanate represented by the following general formula (4) and a dicarboxylic acid represented by the following general formula (6) is; and obtaining the structural unit represented by the general formula (3) by amidating by a decarboxylation reaction between an aromatic diisocyanate represented by the following general formula (4) and a dicarboxylic acid represented by the following general formula (7) is shown:

(where Ar ₂ is defined as described above),

(where Ar ₁ is defined as described above),

(wherein a, b and c are defined as described above),

(where d is defined as described above).

According to the manufacturing process, As has been described above, the amount of phosphorus based condensing agent to be used decreased to allow a lower hygroscopicity of the resin as the hygroscopicity of the polyamide resin to be obtained because the highly reactive aromatic diisocyanate compound as a substance for obtaining an imide compound is used by allowing her to react with the aromatic tetracarboxylic dianhydride, and as a substance for obtaining an amide bond by you enable to react with a butadiene-containing dicarboxylic acid. The amount of ionic impurities whose origin is that of phosphorus based condensing agent can be reduced in the polyamideimide resin in order to enable the insulating properties of the cured resin put them off from being humiliated. Furthermore, since the resin is less compared to the polyamide resin hygroscopic fails, the resin produced is also excellent in terms of hygroscopic 'reflow' properties. In addition, as a structural unit whose origin is derived from the butadiene dicarboxylic acid stems, in the copolymer backbone of the polyamideimide in the cured Resin is formed, the copolymer structure can also be given flexibility become. Accordingly, the resulting cured resin a reduced modulus of elasticity and it is outstanding in terms of its adhesion and flexibility.

According to still another aspect of the present invention, there is provided a polyamideimide resin in which the tetracarboxylic dianhydride is 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride represented by the following formula (8):

The Polyamideimide resin containing the copolymer having the above-described Contains structure is excellent in terms of its flexibility after curing, since the resin has good flexibility. The presence of many aromatic rings gives the resin an excellent property in terms of workability through a laser.

According to the present The invention further provides a polyamideimide resin composition which 10 to 100 parts by weight of an epoxy resin over 100 parts by weight of the polyamideimide resin.

According to one Another aspect of the present invention is a coating film forming material and an adhesive for electronic parts, which is the polyamideimide resin or the polyamideimide resin composition include.

The Polyamideimide resin and the polyamideimide resin composition of the present invention Invention have a low elastic modulus and good adhesion a substrate on during they have an excellent property in terms of their electrical Possess properties and their ability to process through a laser.

The film-forming material and the adhesive for electronic parts under Use of the polyamideimide resin or polyamideimide resin composition can on cheap Be used for an adhesive film, for one way Isolation intermediate film, for a surface protection film or for one solder resistant film for printed Circuit boards, by choosing from the excellent features, as described above, benefits.

The Polyamideimide resin according to the present invention Invention contains a polyamide-imide copolymer represented by the general formula (1) represented structural unit and at least one by the general Formula (2) shown structural unit and one by the general Formula (3) shown structural unit contains.

Ar ₁ and Ar ₂ in the general formula (1) are aromatic groups which may be substituted. Examples of preferred aromatic groups include phenylene, naphthalene, tolylene, tolidine and diphenylmethane groups for Ar ₁ , and biphenyl, benzophenone and naphthalene groups for Ar ₂ . Examples of preferred substituents include alkyl groups having a carbon number of 1 to 5, such as methyl and ethyl groups.

Even though in the general formula (2), the sum a + b + c in the range is from 1 to 100, the value is preferably in the range from 5 to 90, more preferably in the range of 10 to 80. A Value of a + b + c less than 1 tends to achieve flexibility whereas a value of a + b + c exceeding 100, tends to heat resistance and reactivity to diminish.

The relationship a / b is in the range of 1/0 to 0/1, preferably in the range from 1/0 to ¼ and more preferably in the range of 1/0 to 2/3. The ratio a / b with the value of 1/0 tends to reduce the solubility of the resin, whereas the ratio a / b with the value of 0/1 tends to heat resistance of the hardened Resin to improve.

The relationship (a + b) / c is in the range of 1/0 to 0/1, preferably in the range of 95/5 to 2/8, and more preferably in the range from 9/1 to 4/6. The relationship (a + b) / c of 0/1 tends to reduce the electrical resistance whereas the ratio (a + b) / c of 1/0 tends to heat resistance, solubility and the adhesion to diminish.

The Polyamideimide resin according to the present invention Invention contains in the polyamide-imide copolymer structural units k, m and n, which are represented by the general formulas (1) or (2) and (3), where k is an integer not smaller than 1, and m and n are integers that are not less than 0 (n and m are not zero at the same time). The ratio m / (k + m + n) is in in the range of 0 to 0.1 (zero not included), more preferable in the range of 0.01 to 0.07, and even more preferably in the range from 0.02 to 0.05. The insulating property of the polyamideimide resin tends to decrease if the ratio m / (k + m + n) the value 0.1 exceeds while the compatibility with the epoxy resin decreases when the ratio increases Has value 0.

The Resin, the 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride contains which is represented by the formula (8) in the structural unit in the general Formula (1) enjoys preference when flexibility and machining efficiency through a laser in the field of vision.

While that number average molecular weight of the polyamideimide resin according to the present invention is in the range of 2,000 to 50,000, it is preferably in the range of 5,000 to 40,000, more preferably in the range from 6,000 to 30,000 and even more preferably in the range of 8,000 up to 20,000. Film properties, such as heat resistance, tend to decrease if the number average molecular weight becomes less than 2,000, whereas the resin is almost no longer in the reaction solvent soluble becomes when the molecular weight exceeds 50,000, and therefore easily during the Synthesis method insoluble remains. As a result, the workability tends to be poor.

Number average molecular weight is measured by gel permeation chromatography (GPC), and the molecular weight of polyethylene glycol (PEG) is used as the standard for calibration set.

Conveniently, HLC-8120 GPC (manufactured by TOSOH Corp.) is used for the GPC having a column temperature of 40 ° C and a pump flow rate of 0.4 ml / minute. The detector used is an RI detector integrated into the GPC. The data are processed using a calibration curve of the standard PEG of known molecular weight (calibration in a molecular weight range of not less than 1000) to obtain a molecular weight calibrated based on the molecular weight of PEG.
Column used: Super AWM-H + Super AWM-H + Super AW3000
Mobile phase: 10 mM LiBr + N-methylpyrrolidone
Injection volume: 20 μl
Sample concentration: 0.1% (w / w)

Even though the molecular weight distribution usually in the range of 3.0 to 12.0, it is preferably in the range of 2.0 m 10.0 and stronger preferably in the range of 2.0 to 8.0.

The Molecular weight distribution is defined as the ratio (Mw / Mn) of the number-average molecular weight (Mn) by the above GPC Method determined to the weight average molecular weight (Mw).

The Polyamideimide resin of the present invention is according to the Following steps are made, which include: achieving the by the general formula (1) represented by a structural unit Imidieren by means of a decarboxylation reaction between the aromatic diisocyanate represented by the general formula (4) is, and the aromatic tetracarboxylic dianhydride, by the general Formula (5) is shown; achieving the through the general Formula (2) represented by amidation with Help a Decarboxylierungsreaktion between the aromatic Diisocyanate represented by the general formula (4) and the butadiene-containing dicarboxylic acid represented by the general Formula (6) is shown; achieving the through the general Formula (3) represented by amidation with Help a Decarboxylierungsreaktion between the aromatic Diisocyanate represented by the general formula (4) and the butadiene-containing dicarboxylic acid represented by the general Formula (7) is shown: and a copolymerization of the achieved Structural units.

Examples of the aromatic diisocyanate represented by the general formula (4) include phenylene-1,4-diisocyanate, phenylene-1,3-diisocyanate, 2,4-tolylene-diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 '- [2,2-bis (4-phenoxyphenyl) propane] diisocyanate, naphthalene-1,5-diisocyanate, Naphthalene-1,6-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate and 2,2'-dimethylbiphenyl-4,4'-diisocyanate, without but to be limited to that. Each of these aromatic diisocyanates may be alone or as a combination of a variety of them be used.

tolylenediisocyanate is particularly preferred in terms of a balance between the mechanical properties, solubility and cost corresponding performance.

Examples the aromatic tetracarboxylic dianhydride, represented by the general formula (5) include pyromellitic dianhydride, 3,3 ', 4,4'-benzophanontetracarboxylic dianhydride, 3,3', 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-sulfonyldiphthalic, 3,3 ', 4,4'-Biphenyltetracarboxylsäuredianhydrid, 1,2,5,6-Naphthalintetracarboxylsäuredianhydrid, 2,3,5,6-Pyridintetracarboxylsäuredianhydrid, 1,4,5,8-Naphthalintetracarboxylsäuredianhydrid, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane and butane tetracarboxylic dianhydride, but without being limited to it. Each one of them can be alone or used as a combination of a plurality thereof become.

2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, the above an excellent property in terms of machinability by a laser, is preferred among them because of its ether linkage has a flexibility.

Tricarboxylsäureanhydride (such as trimellitic anhydride, 3,3,4-Benzophenontricarboxylsäureanhydrid and 2,3,4'-diphenylethertricarboxylic anhydride) can additionally to the above dianhydrides, if necessary is.

The are dicarboxylic acids represented by the general formulas (6) and (7) an acrylonitrile-butadiene copolymer and butadiene with carboxyl groups at both ends of the same. The number average molecular weight of these compounds is preferably in the range between 1000 to 5000, and compounds known in the art may be used become.

Examples of the acrylonitrile-butadiene copolymer represented by the general formula (6) with carboxyl groups at both ends include polymers from the series from Hycar RLP (for example CTBN 1300x8, CTBN 1300x13, CTBN 1300 × 31 and CTBNX 1300x9), manufactured by Ube Industries Ltd., but without limitation be.

Examples the butadiene copolymer represented by the general formula (7) with carboxyl groups at both ends include polymers from the series from Nisso-PB (for example, C-1000) manufactured by Nippon Soda Co. and polymers from the series of Hycar RLP (for example, CTB 2000 × 162) from Ube Industries Ltd., without being limited to it.

One Each of these polymers can be used alone or as a combination of a plurality of them are used.

aliphatic dicarboxylic acids (such as succinic acid, glutaric, adipic acid, azelaic acid, decanedicarboxylic, Dodecandicarboxylsäure and dimer acids) and aromatic dicarboxylic acids (Isophthalic, terephthalic acid, phthalic and naphthalenedicarboxylic acid) can additionally to the above dicarboxylic acids be used if necessary.

The Total amount represented by the general formulas (6) or (7) dicarboxylic acid, which is to be compounded is preferably 20 to 80% by weight, more preferably 30 to 70 weight percent, and more preferably 40 to 60 weight percent relative to the polyamide-imide copolymer. Adhesion and the flexibility tend to decrease when the amount that leads to a connection is less than 20 weight percent, while the heat resistance tends to worsen when the amount of mixture Exceeds 80 weight percent.

in the Under the present invention, the mixing ratio between the aromatic diisocyanate and the aromatic tetracarboxylic dianhydride and the mixing ratio between the aromatic diisocyanate and the dicarboxylic acid for Synthesis of the polyamide imide copolymer determined by the ratio of Total number of isocyanate groups to the total number of acid anhydride groups and the carboxyl groups in the dicarboxylic acid. This ratio is preferably in the range of 0.7 to 1.3, more preferably in the range from 0.8 to 1.2 and even stronger preferably in the range of 0.9 to 1.1. It will be rather difficult sufficiently increase the molecular weight of the resin when the relationship is less than 0.7 or if it exceeds 1.3.

The Polyamide-imide copolymers of the present invention having the the general formulas (1), (2) and (3) represented structural units can by simultaneously polymerizing the aromatic diisocyanate, of the aromatic tetracarboxylic dianhydride and dicarboxylic acid getting produced; or you can can be achieved by reacting an excess amount of the aromatic Diisocyanate with the aromatic tetracarboxylic acid dianhydride or the dicarboxylic acid a polyimide or polyamide oligomer having isocyanate groups at the ends followed by polymerization by the addition of a residue of aromatic tetracarboxylic dianhydride or dicarboxylic acid.

High polar, aprotic solvents such as NMP (N-methylpyrrolidone), DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide) and DMSO (dimethyl sulfoxide) are preferred as an organic solvent for the Synthesis of a polyamide-imide copolymer according to the present invention used. Aliphatic hydrocarbons such as cyclohexane, Pentane and hexane, aromatic hydrocarbons such as benzene, Toluene and chlorobenzene, ethers such as THF (tetrahydrofuran), diethyl ether and ethylene glycol diethyl ether, ketones such as acetone, methyl ethyl ketone and 4-methyl-2-pentanone and esters such as methyl propionate, ethyl acetate and butyl acetate also be used as long as reaction substrates and target products in these solvents sufficiently soluble are. These solvents can to be used as a mixture.

The amount of these organic solvents to be used is preferably 0.8 to 5 times (by weight) the polyamideimide resin to be formed. A share, is less than 0.8 times, causes an excessively high concentration of the polymer in the synthesis process, which makes it difficult to carry out the stirring and thus the synthesis, while a proportion exceeding 5 times the value tends to Reduce reaction rate.

The Reaction temperature for obtaining the polymer is usually 80 up to 210 ° C, preferably 100 to 190 ° C and stronger preferably 120 to 180 ° C. Although the temperature from the beginning to the end of the reaction can be constant, the temperature in the initial stages of the Reaction be low, with a subsequent increase in temperature. A reaction temperature of below 80 ° C causes a low reaction rate, what an overly long Reaction time, which may not cause one sufficient molecular weight leads, while a temperature exceeding 210 ° C, In the course of the reaction, a gel tends to form.

The Reaction time is usually 1 to 10 hours, preferably 2 to 5 hours, taking the progression takes into account the polymerization.

One Catalyst can be added to the reaction system if this is required. Examples of available catalysts include tertiary Alkylamines such as N, N, N ', N'-tetramethyl-1,3-butanediamine, Triethylamine and tributylamine; condensed cyclic amines such as about 1,4-diazabicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] und-7-ene; Phosphorus compounds such as 1-phenyl-2-phosphorene-1-oxide; and 3-methyl-1-phenyl-2-phosphorene-1-oxide; and metals like Alkali metals, alkaline earth metals, tin, zinc, titanium and cobalt.

The A polyamideimide resin composition according to the present invention contains 100 parts by weight of polyamideimide resin of the present invention and 10 to 100 parts by weight of an epoxy resin. The solvent resistance, the adhesion and the antihygroscopic 'reflow' ability the resulting hardened Resin composition can be improved by using the epoxy resin. The amount of the epoxy resin to be used is 10 to 100 parts by weight, preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight compared of 100 parts by weight of the polyamideimide resin. The durability across from solvents and the anti-reflow ability of the cured resin tend to decrease when the amount of epoxy resin is less than 10 parts by weight while the Shelf life, the heat resistance and the adhesion of the hardened Resin tends to decrease when the amount of epoxy resin is 100 Exceeds parts by weight.

Examples of according to the present Invention available Epoxy resin includes bisphenol A epoxy resins such as Epicron 840, 840-S, 850, 850-S, 860, 1050, 1055, 3050, 4050, AM-020-P and AM-030-P; bisphenol F epoxy resins such as Epicron 830, 830-S and 835; Cresol novolac epoxy resins such as Epicron N-660, N-665, N-673, N-680, N-660-LE and N-665-LE; Phenol novolac epoxy resins such as Epicron N-740, N-770, N-775, N-740-80M and N-770-70M; and flexible epoxy resins such as Epicron TSR-960, TSR-601 and 1600-75X (all are available from Dainippon Ink and Chemicals, Inc., manufactured); and bisphenol A epoxy resins such as Epicoat 825, 827, 828, 828EL, 828XA, 834, 1001, 1002, 1003, 1055, 1004, 1004AF, 1007, 1009 and 1010 made by Japan Epoxy Resins Co., Ltd. However, the epoxy resin is not limited thereto. Each of the epoxy resins can be alone or as a combination of at least two of them be used.

One curing Agent may be added to the polyamideimide resin composition according to the present invention Invention added become. Known hardeners, the for Epoxy resins can be used, and can be used Examples thereof include amines, polyamide resins, novolac resins and acid anhydrides.

Examples The amines include aromatic polyamines such as ethers 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and p-phenylenediamine; aliphatic polyamines such as diethylenetriamine, Triethylenetriamine, meta-xylenediamine and bis (4-amino-3-methylcyclohexyl) methane; Piperidine, pyrrolidine, imidazole and their derivatives; and secondary and tertiary amines such as triethylamine, N, N, N ', N'-tetramethylhexamethylenediamine, 1,8-diazabicyclo [5.4.0] undecene, 1,4-diazabicyclo [2.2.2] octane and picoline.

Examples of the polyamide resin include reaction products of aliphatic ones dicarboxylic acids, dimer and trimer acids with polyamines.

Examples of the novolac resins include low molecular weight resin compositions obtained by condensation of phenol and formaldehyde and condensation of a Mi. obtained from phenol, cresol and dihydroxybenzene with formaldehyde.

Examples of the acid anhydride contain acid anhydrides such as phthalic anhydride, Trimellithsäureanhydride, Pyrromellithsäureanhydrid, Benzophenontetracarboxylsäureanhydrid, methyltetrahydrophthalic and succinic anhydride and mixtures thereof.

The Method for The addition of the epoxy resin to the polyamide-imide resin of the present invention is not subject to any special restrictions. For example, will the epoxy that added should be previously dissolved in the same solvent as that Solvent, that for the preparation of the polyamideimide resin has been used, and the solution becomes the polyamideimide resin solution added. alternative For example, the epoxy resin may be added directly to the polyamide-imide resin.

organic and inorganic fillers, surfactants Substances such as antifoaming agents and leveling agents, dyes like coloring Agents and pigments, heat stabilizers, anti-aging agents, fire-retardant Substances and lubricants can to the polyamide-imide resin and to the polyamide-imide resin composition the present invention for improving the processability the coating and film properties before and after formation added to the coating film become.

The A polyamideimide resin and the polyamideimide resin composition according to the present invention Invention are favorable and advantageous to be used as film-forming materials, used for the production of insulating films, surface protective films, solder resistant films and adhesive films on printed circuit boards and as adhesives for electronic Parts are used.

EXAMPLES

Even though the invention in the following with reference to examples detailed is described, the invention is by no means based on these examples limited.

EXAMPLE 1

Into a 500 mL separable glass flask equipped with a stirrer, a reflux column and a nitrogen inlet tube are charged 8.88 g (2.5 mmol) of Hycar CTBN 1300 × 8 manufactured by Ube Industries Ltd.) as an acrylonitrile-butadiene copolymer having carboxyl groups at both ends, 2.10 g (0.5 mmol) of Hycar CTB 2000 × 162 (manufactured by Ube Industries Ltd.) as a butadiene copolymer having carboxyl groups at both ends and 66.2 g of N-methylpyrrolidone (hereinafter abbreviated to NMP) and the mixture is dissolved in a homogeneous manner by heating at 60 ° C. To this are added 24.46 g (47 mmol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter abbreviated to BSAA) as the aromatic tetracarboxylic acid dianhydride, and then after dissolution of compound 8, 71 g (50 mmol) of tolylene diisocyanate (a mixture of a 2,4-substituted compound and a 2,6-substituted compound, which will be abbreviated to TDI hereinafter) as an aromatic diisocyanate. The mixture is heated to 170 ° C and then stirred for a period of 2 hours. The reaction is complete when it is confirmed that the absorbance peak values of the isocyanate at 2270 cm ^-1 and the acid anhydride at 1854 cm ^-1 in the IR spectrum have disappeared. The reaction system is cooled to room temperature after completion of the reaction in a water bath.

The reaction solution is diluted with NMP and the polymer solution obtained is under vigorous Stir poured into methanol, to enable the resin to strike down and to leave. The precipitated resin is isolated by filtration. The resulting resin is further with Washed methanol and at 60 ° C. while a period of 48 hours using a hot air circulating dryer dried to obtain 36.6 g (yield 92%) of a resin powder.

The IR spectrum confirms that the structure of the obtained resin powder is a desired polyamideimide resin, the IR spectrum showing peaks at about 1778 cm ^-1 and 1726 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 12,000 and 4.2, respectively by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 2

One Resin powder (40.5g, yield 92%) is in the same manner as obtained in Example 1, except that 5.33 g (1.5 mmol) Hycar CTBN 1300 × 8; 10.50 g (2.5 mmol) Hycar CTB 2000 x 162; 72.71 g of NMP, 23.94 g (46 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 11000 and 3.5, respectively by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 3

One Resin powder (43.8g, yield 93%) is in the same manner as obtained in Example 1, except that 8.88 g (2.5 mmol) Hycar CTBN 1300 × 8; 10.50 g (2.5 mmol) Hycar CTB 2000 x 162; 77.26 g NMP, 23.42 g (45 mmol) BSAA and 8.71 g (50 mmol) TDI.

The IR spectrum confirms that the structure of the resulting resin powder is a desired polyamideimide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the obtained resin are at 10,000 and at 3.5, as is by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 4

One Resin powder (45.7g, yield 91%) is in the same manner as obtained in Example 1, except that 1.78 g (0.5 mmol) of Hycar CTBN 1300 x 8; 21.00 g (5.0 mmol) Hycar CTB 2000 x 162; 82.0 g NMP, 23.16 g (44.5 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 12000 and 4.0, respectively by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 5

One Resin powder (53.5g, yield 95%) is in the same manner as obtained in Example 1, except that 8.88 g (2.5 mmol) Hycar CTBN 1300 × 8, 21.00 g (5.0 mmol) Hycar CTB 2000 x 162, 91.1 g NMP, 22.12 g (42.5 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 13,000 and 4.3, respectively by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 6

One Resin powder (52.7g, yield 95%) is in the same manner as obtained in Example 1 with the exception that 13.31 g (3.75 mmol) Hycar CTBN 1300 x 8; 15.75 g (3.75 mmol) of Hycar CTB 2000 x 162; 89.84 g of NMP, 22.12 g (42.5 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are at 12500 and at 4.5, as is by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 7

One Resin powder (60.7g, yield 95%) is in the same manner as obtained according to Example 1 with the exception that 17.75 g (5.0 mmol) Hycar CTBN 1300 x 8; 21.00 g (5.0 mmol) Hycar CTB 2000 x 162; 102.42 g NMP, 20.82 g (40.0 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 15,000 and 5.0, respectively by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 8

One Resin powder (65.2g, yield 95%) is in the same manner as obtained in Example 1, except that 1.78 g (0.5 mmol) Hycar CTBN 1300 × 8; 42.00 g (10.0 mmol) Hycar CTB 2000 x 162; 72.70 g NMP, 20.56 g (39.5 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 14,000 and 4.1, respectively by GPC using polyethylene glycol as reference material is determined.

EXAMPLE 9

One Resin powder (68.7g, yield 92%) is in the same manner as obtained in Example 1, except that 8.88 g (2.5 mmol) Hycar CTBN 1300 × 8; 42.00 g (10.0 mmol) Hycar CTB 2000 x 162; 118.7 g of NMP, 19.52 g (37.5 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 17,000 and 4.1, respectively by GPC using polyethylene glycol as reference material is determined.

Comparative Example 1

One Resin powder (44.8g, yield 92%) is in the same manner as obtained in Example 1 with the exception that Hycar CTBN 1300 × 8 not used and that 21.00 g (5.0 mmol) of Hycar CTB 2000 x 162; 79.70 g NMP, 23.42 g (45.0 mmol) BSAA and 8.71 g (50 mmol) TDI become.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 11000 and 3.5, respectively by GPC using polyethylene glycol as reference material is determined.

COMPARATIVE EXAMPLE 2

One Resin powder (58.5g, yield 94%) is in the same manner as obtained in Example 1 with the exception that 26.63 g (7.5 mmol) Hycar CTBN 1300 x 8; 10.5 g (2.5 mmol) Hycar CTB 2000 x 162; 72.70 g of NMP, 20.82 g (40.0 mmol) BSAA and 8.71 g (50 mmol) TDI.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 12,000 and 3.5, respectively by GPC using polyethylene glycol as reference material is determined.

COMPARATIVE EXAMPLE 3

One Resin powder (40.5g, yield 92%) is in the same manner as obtained in Example 1 with the exception that Hycar CTBN 1300 × 8 is not used and that 35.50 g (10.0 mmol) Hycar CTB 2000 × 16; 97.5 g NMP, 23.42 g (45.00 mmol) BSAA and 8.71 g (50 mmol) TDI become.

An IR spectrum confirms that the structure of the resulting resin powder is a desired polyamide-imide resin, with the IR spectrum showing peak values at about 1780 cm ^-1 and 1730 cm ^-1 , which are assigned to the imide group, and a peak at about 2240 cm ^{. 1} , which is assigned to the nitrile group.

The number average molecular weight and molecular weight distribution of the resulting resin are 15,000 and 4.0, respectively by GPC using polyethylene glycol as reference material is determined.

The Components and their mixing ratios, which in the examples 1 to 9 and used in Comparative Examples 1 to 3 are shown in Table 1.

EXAMPLE 10

To 100 parts by weight of a resin fraction in the polyamideimide resin obtained in Example 1 is added 60 parts by weight of an epoxy resin (Bisphenol A epoxy resin, Epicron 840S manufactured by Dainippon Ink and Chemicals Inc.), 34 parts by weight of a curing agent (Tamanol P-180 phenol resin, e.g. manufactured by Arakawa Chemical Industries Ltd.) and an amine catalyst (Curesol C11Z, available from Shiko ku Chemicals Co.), and a polyamideimide resin composition containing 40% by weight of a non-volatile fraction is obtained by diluting the mixture with N, N-dimethylacetamide.

EXAMPLE 11

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same way as that of example 10 with the exception that the resin obtained in Example 2 was used as the Polyamideimide resin is used.

EXAMPLE 12

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 3 was used as the Polyamideimide resin is used.

EXAMPLE 13

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 4 was used as the Polyamideimide resin is used.

EXAMPLE 14

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 5 was used as the Polyamideimide resin is used.

EXAMPLE 15

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 6 was used as the Polyamideimide resin is used.

EXAMPLE 16

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 7 was used as the Polyamideimide resin is used.

EXAMPLE 17

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 8 was used as the Polyamideimide resin is used.

EXAMPLE 18

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 with the exception that the resin obtained in Example 9 was used as the Polyamideimide resin is used.

COMPARATIVE EXAMPLE 4

To 100 parts by weight of a resin fraction in a resin (Type-0, manufactured by Tomoegawa Paper Co.) mainly comprising an aromatic polyamide-acrylonitrile-butadiene copolymer, 60 parts by weight of an epoxy resin (Bisphenol A epoxy resin, Epicron 1055, manufactured by Dainippon Ink and Chemicals Inc.) A curing agent (a Tamanol P-180 phenolic resin manufactured by Arakawa Chemical Industries Co.) and an amine catalyst (Curesol C11Z manufactured by Shikoku Chemicals Co.) are added to obtain a polyamideimide resin composition containing 40% by weight one non-volatile fraction by diluting the mixture with a mixed solvent of methyl ethyl ketone and N, N-dimethylacetamide.

COMPARATIVE EXAMPLE 5

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 except that obtained in Comparative Example 1 Resin is used as the polyamideimide resin.

COMPARATIVE EXAMPLE 6

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 except that obtained in Comparative Example 2 Resin is used as the polyamideimide resin.

COMPARATIVE EXAMPLE 7

A Polyamideimide resin composition which is not 40% by weight of one volatile Contains fraction, is achieved in the same manner as that of Example 10 except that obtained in Comparative Example 3 Resin is used as the polyamideimide resin.

The in Examples 10 to 18 and Comparative Examples From 4 to 7 obtained resin compositions are tested as follows.

PREPARATION OF ADHESIVE FILMS

The obtained in Example 10 Polyamidimidharzzusammensetzung is on applied a polyethylene terephthalate film (having a thickness of 25 microns), its a surface has been treated with silicone, and it will be an adhesive film with a thickness of 25 microns by drying at 120 ° C while made a period of 10 minutes. Adhesive films will too prepared using the in Examples 11 to 18 and the Polyamideimide resin compositions obtained in Comparative Examples 4 to 7.

MEASUREMENT OF THE ELASTICITY MODULE OF THE ADHESIVE FILM

To the complete hardening of the above-obtained adhesive film by heating at 180 ° C during a For a period of 90 minutes, the modulus of elasticity is determined using a dynamic viscoelastometer (trade name DMS 120, available from Seiko Instruments Co.). The heating rate is 10 ° C / minute.

MEASURE THE ADHESIVE FORCE OF THE ADHESIVE FILM (ICP-TM-650 2.4.9)

Of the The adhesive film obtained above is applied to a side surface of copper of a two-sided Substrate (polyamide / copper) glued by pressing, and he will hardened, by standing at 180 ° C while is heated for a period of 90 minutes. The film obtained gets a 90 ° peel test subjected to the adhesive force to measure the movie.

MEASURE THE SPECIFIC THROUGH RESISTANCE THE ADHESIVE FILM

To the complete Curing of the above-obtained adhesive film by heating at 180 ° C during a For a period of 90 minutes, a conductive paste is applied to the film as Electrodes are applied to the volume resistivity to measure the movie.

MEASUREMENT OF THE HYGROSCOPIC COEFFICIENT THE ADHESIVE FILM

To the complete hardening of the above-obtained adhesive film by heating at 180 ° C during a Duration of 90 minutes, the film is in a constant environment Temperature and constant humidity (85% RH = relative humidity = relative humidity) at 85 ° C while a period of 48 hours, and then the hygroscopic Coefficient of the adhesive film measured by the Karl Fischer method.

PRELOAD TEST OF THE ADHESIVE FILM UNDER INCREASED HUMIDITY

Comb-shaped patterns having a width of lines / pitch of 100 μm / 100 μm are formed on a polyimide film, and a sample is prepared by adhering the adhesive film to the polyimide film. The insulation resistance of this sample is measured for a period of 1000 hours under the condition of 60 ° C / 95% RH while applying a DC voltage of 15V. The sample which maintains an insulation resistance of not less than 5 × 10 ⁸ Ω for 1000 hours is evaluated as good (O), the sample showing a decrease in resistance below 5 × 10 ⁸ Ω during the measurement is judged to be relatively good (Δ), and the sample showing a resistance of less than 5 × 10 ⁸ Ω immediately after the start of measurement is evaluated as poor (×).

HYGROSCOPIC REFLOW TEST OF ADHESIVE FILM

One Three-layer test substrate is prepared using the above adhesive film produced. The test substrate is allowed to absorb the moisture absorb it by subjecting it to a condition of 30 ° C / 60% RH for a period of 168 Hours, and it allows the test substrate to then through a reflow oven (peak temperature 260 ° C) three times to happen. A foaming (Swelling) in the substrate is, if at all, visual Test confirmed, and the sample that shows no foaming, is rated as good (O) while the foamed Sample is rated as poor (x).

Table 2 shows that the polyamideimide resin compositions in the Examples have the same elastic modulus levels as those of the polyamide resin compositions in Comparative Example 4 and the polyamideimide resin compositions in Comparative Examples 5 to 7, and they have an excellent adhesion force to the substrate, while the insulating properties thereof are excellent with a large volume resistivity. Moreover, the polyamideimide resin compositions in the examples have lower hygroscopicity than those of the polyamide resin in the comparative examples, while the former are also excellent in the properties of bias under increased humidity and hygroscopic reflow characteristics.

Claims (8)

A polyamideimide resin comprising a structural unit represented by the following general formula (1) and at least one structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (3), wherein the number k of the structural unit, represented by the general formula (1), the number m of the structural unit represented by the general formula (2), and the number n of the structural unit represented by the general formula (3) included in the polyamide resin satisfying the relationship 0 <m / (k + m + n) ≦ 0.1 containing the resin, a polyamide-imide copolymer having a number-average molecular weight of 2,000 to 50,000:

wherein each Ar ₁ and Ar _{2 represents} an aromatic group which may be substituted,

wherein Ar _{2 is} defined as described above and each of a, b and c is an integer of 0 to 100 with the following relations; Ratio a / b in the range of 0/1 to 1/0, ratio (a + b) / c in the range of 1/0 to 0/1, and the sum (a + b + c) is in the range from 1 to 100,

wherein Ar _{2 is} defined as described above and d is an integer of 1 to 100. A process for producing the polyamideimide resin according to claim 1, which comprises the steps of: obtaining the structural unit represented by the general formula (1) by imidizing by means of a decarboxylation reaction between an aromatic diisocyanate represented by the following general formula (4) and an aromatic tetracarboxylic acid dianhydride represented by the following general formula (5); obtaining the structural unit represented by the general formula (2) by amidating by a decarboxylation reaction between an aromatic diisocyanate represented by the following general formula (4) and a butadiene-containing dicarboxylic acid represented by the following general formula (6 ) is shown; and obtaining the structural unit represented by the general formula (3) by amidating by a decarboxylation reaction between an aromatic diisocyanate represented by the following general formula (4) and a butadiene-containing dicarboxylic acid represented by the following general formula ( 7) is shown

where Ar _{2 is} defined as described above,

where Ar _{1 is} defined as described above,

where a, b and c are defined as described above,

where d is defined as described above. Polyamideimide resin obtained by the method of Preparation of the polyamideimide resin can be achieved according to claim 2 can. A polyamideimide resin according to claim 3, wherein the tetracarboxylic dianhydride is 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride represented by the following formula (8):

Polyamideimide resin composition which is 10 to 100 Parts by weight of an epoxy resin compared to 100 parts by weight the polyamideimide resin according to any one of the claims 1, 3 and 4. Film-forming material containing the polyamideimide resin according to any the claims 1, 3 and 4. Film-forming material containing the polyamideimide resin composition according to claim 5 has Adhesive for electronic parts comprising any of the polyamideimide resins according to any one of the claims 1, 3 and 4 and the polyamideimide resin composition according to claim 5 includes.